Hydrogenation catalyst and use in oxo process



June 24, 1958 R. B. MASON ET AL 2,840,519

HYDROGENATION CATALYST AND USE IN OXO PROCESS Filed July 25, 195e PURE2 la lo l? I2 T 2O 8 :Jl T

l L 34`HGAS I Mii- 30 36) 38 a? H2+C0 41T "24' 4-HB2 l cATALYsT I 2 26 298 l 39 A 3 oLEFlN T 2523581 f 2 6l M l H 0 43 63 2 f 4h20 Y l BoTToMs se v 62, H2 2 Ralph B. Mason Rhea N. watts lnvemors By M Attorney atent HYDRoGENATIoN CATALYST AND USE 1N 5 oxo lrnocnss lRalph Burgess VMason, Denham Springs, and Rhea N.

Watts, St. Francisville, La., assignors to Esso Research and Engineering Company, a corporation of Delaware The present invention relates to the preparation of 15 oxygenated organic compounds by the reaction of olenic carbon compounds with hydrogen and carbon monoxide in the presence of a carbonylation catalyst. More speciiically, this invention relates to an improved process for increasing the selectivity of the process to useful alcohols, and the maintenance of a high level of activity of the -hydrogenation catalysts while improving the strength of the catalyst employed in hydrogenating the aldehyde produced in the vfirst stage of the reaction.

This application is 'a continuation-in-part of the application, Serial Number 353,590, tiled May 7, 1953', and now abandoned.

Itis now Well known in the art that oxygenated 'organic compounds may be synthesized from oleiinic organic compounds by reaction of the latter with carbon monoxide and hydrogen in the presence of a catalyst containing lcobalt or other carbonyla'tion catalyst in 'an 'essentially three-stage process; In the lirst stage the oleiinic material, catalyst, and synthesis gases are reacted under .pressure to give a product consisting predominantly of aldehydes containing one more carbon atom than the ol'eiinic material, as well as a certain amount of secondary reaction products, polymeric material, etc. This oxygenated organic mixture, which contains in solutioncompounds of the metal catalyst may be treated in a second stage with heat to cause decomposition and removal of the soluble catalytic material from the organic mixture. The catalyst-free material may then be hydrogenated in a hydrogenation stage to the corresponding alcohol, or it may be oxidized to the corresponding carboxylic a'cid.

This carbonylation reaction provides a particularly attractive method for the preparation of valuble primary alcohols, which find large outlets, particularly as intermediates for plasticizers, detergents, and solvents. Not only long and short chained oleiinic hydrocarbons, but also, most other types of organic compounds containing at least one olefinie double linkage, such as unsaturated acids, esters, alcohols, ketones, etc., are susceptiblet this type of reaction. 55

The catalyst for the iirst stage of the reaction, where olefinic material is converted into aldehydes, is usually added in the form of salts of the catalytically active metal with high molecular weight organic acids, such as oleic, stearic, naphthenic, etc. Examples of such catalyst salts or soaps are cobalt oleate, stearate, naphthenate and the like. These salts are soluble in the liquid olefin or olefinparaiiin feed, and may be supplied tok the first stage as dissolved in the feed or as hydrocarbon solution.

As the synthesis gases are consumed at equivalent or 5,5 equimolar rates, synthesis gas components are usually added at equimolar proportions of H2 and CO, though it has been suggested to use both an excess of hydrogen and an excess of CO. The conditions for reacting olelinic compounds with hydrogen and carbon monoxide vary somewhat in accordance with the nature of the oleinic feed, but the reaction is generally conducted at pressures of about 3000 pounds per square inch and at tempera'- A OM 2,840,619 Patented vJune 24, 1258 `sion of oleiins to oxygenated compounds has been effected, the products and the unreacted material `areg'er'lerally withdrawn vto a catalyst removal zone,rwliere d ssolved catalyst is removed from the mixture by thermal treatment. l

'From the carbonylationcatalyvst removal Zonethe alde- 'h'yde product is passed to a hydroger'iationY vzoner for'c'ofiversion to alcohols. The hydrogenation stage 'may 'bea xed bed koperated at conventional hydrogenationzoditions which include temperatures, pressures and g''snd 'liquid feed rates approximately within the ranges specified above 'for the first stage. lt is to the catalytic .treatment of the aldehyde product, in particular to the nature of the hydrogenation catalyst, that the present invention applies.

In the past it'has been suggested to employ as Oxo iiydrogenation catalyst, such catalysts as nickel, cobalt, copper chromite, oxides and sulfides of tungsten and molybdenum, etc. all of which may be, if desired, supported on a suitable carrier. All of these catalysts, however, have not been entirely satisfactory, due to the nature of the carbonyl'a'tion reaction and to the products present in the stream to the hydrogenation plant.

An important problem involved in the aldehyde-alcohol synthesis process is the presence of Water in amounts up to as much as 10% `in the hydrogenation zone.V Water results in part from the nature of the secondaryjreactios occurring in the first stage. Thus, aldehydes may in part be further reduced inthe iirst stage to form yalcohj'nl's which in turn react with further quantities of aldehydes, with water formed as a byproduct. Similarly, Cannizzaro type reactions followed by esterification produce water, as also intra and intermolecular dehydration.

However, not only is water formed in the first stage of the process, but it also has been found that hydrogenaytion itself is considerably improved when water, in amounts up to v10% is added to the hydrovstagef. The selectivity to the desired alcohols is significantly creased, the water possibly functioning to repress'ce'tal formation and alcohol dehydration. v

With the` presence of water in thehydrogenatioirs'tag'e it becomes necessary, therefore, to employ a c'atalystthat is not affected by water', either in activity o r in physical strength; High mechanical strength is of particular importance in commercial operations which involve the use of vfixed catalyst beds 'of considerable height and weight to `which 4the lower catalyst layers are subjected. In addition, the hydrogenation stage is a liquid phase operation in which catalyst is subjected to the action of high velocity liquid streams which tend to disintegrate the, catalyst, leading to channeling and plugging in thereactor when a structurally weak catalyst is employed. 4The need of a Water-resistant catalyst of satisfactory activity, which may be used at conditions conducive to substantially comf plete conversion of aldehydes into alcohol, therefore, has been stronglyfelt in the synthesis art. The present inl venti'on llsv this need. y l Y y A step forward in the art was taken by the proposal that sulfactive catalyst suitably supported, such as molybn denuin slfide on activated carbon, be employed. These types of catalyst have the necessary Vmechanical strength, but in general require higher reaction temperatures than metal catalyst, and too high temperatures decrease alcohol selectivity. Also, they have the disadvantage that when theyy are freshly suliided or regenerated for an extended period of time, the resultant alcohols are contaminated with sulfur and require rerunning, and this tendency `range ofthe alcohol product.

. Type Hydrogen factive catalysts isthat, in particular when relatively low `molecular weight aldehydes are hydrogenated, excessive :amounts of hydrocarbons are formed, `due to the relatively high hydrogenation temperatures required. These hydro- .carbons are very difficult to separate byY distillation and fractionation, for some `of the hydrocarbons boilin the Thus, when a butylene fraction is passed as feed to the carbonylation stage to form a mixture of amyl aldehydes, and this material is hydrogenated over a sulfactive catalyst consisting of molybdenum sulfide supported on activated char, and ,alcohol product contaminated with 5,-10% hydrocarbons,

most of which boil in the alcohol range, is obtained. On

the otherzhand, when catalysts such asnickel or copper Lchromite are employed to hydrogenate such aldehyde product, vsubstantially lowerrtemperatures may be em `Aployed, 1ittle or no hydrocarbon is formed in the hydro'- genation, but the catalysts have very poor physical strength, particularly in the presence of water, which is a desirable additive to aid alcohol selectivity. This is clearly shown in the data below:

I'V HYDROGENATION OF C5 OXO ALDEHYDES [510 wt. percent added water. t 3 litcr shaker autoclave unit.)

. Molyb- Catalyst Com. Copper denurn Nickel Chromite Sulfide on Char.

Methanized Ccmmerclal Temperature, F, Pressure, P. s. i. g--

`Hours ol Run 6..

Product Carbonyl No 1.5. Wt.V Percent Hydrocarbons in Distilled Alcohol 8.0. Used Catalyst Crushing Strength, Lbs.:

Maximum 36.0. 20.0. 27.2.

It is the principal purpose of the present invention, therefore, to provide an improved catalyst for the hydrogenation of aldehydes formed by the carbonylation reaction.

A more specific purpose and object of the present invention is to improve the operation of the liquid phase hydrogenation stage of the alcohol synthesis process, particularly when water is present.

It is `a. still further object of the present invention to prepare catalysts suitable for hydrogenating aldehydes, particularly in the presence of.water, which shall have `retained essentially `their full activity while having been `treated so as to increase their physical strength.

Other and further objects and advantages of the invention. will appear hereinafter.

In accordance withthe present invention, the` aldehyde Vproduct from the first stage of the synthesis is hydro- 4the catalyst, forms a catalyst of high activity and physical strength, which will not disintegrate in the presence of water, as the unbound catalyst, and catalysts pelleted by conventional methods, such as mechanical pilling with h punches and dies, or extrusion of pastes followed by drying will, nor will it show reduced activity.

In the hydrogenation of aldehydes selectively to alcohols, copper chromite catalysts have shown great ypromise except that pellets formed by conventional procedures quickly vdisintegratein service. This condition `is agwater present.

added to the process. The use of metal binders in pilling, which prevent pill disintegration in service, even in the presence of water while still maintaining a high degree of catalyst activity, is a means of securing the benefits of the high selectivity of this catalyst without its disadvantages.

For example, a copper chromite catalyst prepared by the Adkins technique disintegrated almost completely in the autoclave hydrogenation of a C5 oxo aldehyde at 450 F. with l0% water present. Also, the disintegration was of the same magnitude when the operation was conducted in the absence of added water. The same catalyst pilled with 20% aluminum and then heated in hydrogen for 7 to 8 hours at approximately 850 F. but for a short period at about l200 F. was not deactivated nor did it disintegrate in the more severe condition with Furthermore, the used catalyst had an average side crushing strength of 9.4 pounds as compared to 8 pounds for the preparation with aluminum prior to the heat treatment and 4.2 pounds for the preparation without aluminum.

The employment of copper, nickel, and cobalt chromite hydrogenation catalysts is well known in the art; even in the comparatively recent Oxo art, the use of these catalysts has been proposed. However, as pointed out, it has been found that the process of making the catalyst plays a vital role in the suitability of the catalyst for the continuous Oxo hydrogenation service, for the stronger the catalyst the longer may the operation be carried out.

In general, in the present invention, hydrogenation catalysts of the reduced metal or mixed oxide type, such as copper chromite, usually requiring an activation following reduction with hydrogen, may be employed. A suitable method for introduction of a metal binder such as aluminum may consist in the usual thermal treatment or activation, following which the iinely divided binder is mechanically mixed with the catalyst component and the mixture subjected to heat treatment at or near the activation temperature of the catalyst. Alternatively the non-activated catalyst may be mixed with the binder, and the mixture subjected to heat treatment at or near the activation temperature of the catalyst.

A suitable bonding agent is aluminum. Metals whose i melting or sintering points are markedly above or -below the activation temperature of the hydrogenation catalysts are considerably less desirable in that the catalyst must either suffer deactivation or fail to be properly bonded during the sintering treatment necessary for bonding the metal and catalyst.

It is well known in the art that for certain hydrogenation processes, copper oxide serves as the catalytic oxide. Pellets have been produced in which the copper oxide is bonded to high melting metals such as nickel, and iron. However, the high temperatures needed for proper bonding of catalyst and metal tend to deactivate the catalyst. Indeed under certain operating conditions which require an extremely strong pellet, it has been expedient to sacritice some of the catalytic activity in the interests of producing a strong pellet.

The present invention oiers a method of producing a catalyst pellet of great strength, while not adversely effecting the catalytic activity. Hence, a hydrogenationl catalyst of undiminished activity and superior strength qualities is produced. Such a combination is particularly advantageous in liquid phase hydrogenation reactions.

Though substantially any hydrogenation catalyst may be thus bonded by finely-divided metals, the most useful application of the present invention is with supported rcduced metal catalysts and with mixed oxide hydrogenation catalysts.

The process of the invention in all its stages may be carried out by conventional means in any suitable equipment. The design and operation of such equipment will he brieily described hereinafter with reference` to the acyc'xtiipanying vdrawing which illustrates schematically Va Ysuitable system of this type.

`Referring now tothe iigure, an oletinic hydrocarbon lhaving 'onelcarbonatomiess than the'number of carbon atoms in the' desired resulting-alcohol and containing dissolved/a catalyst promoting the reactionof oleiinic compoundswith carbon monoxide/and hydrogen to-form oxy- "genated organic compounds is fed to the `lower portion of primary reactor 1 through' feed line 2. Any conventional type catalyst such as cobalt s tearate, naphthenate, oleate, iron linoleate, etc., may Uef'used. Catalyst malte-up dissolved in olelin feed may be added to the main olefin feed line 2 through line 3. The concentrations of catalyst and the proportions of the catalyst-containing feed Vto the non-catalyst containing feed are such that the conandat ate'mperature of fromabout Z50-450?. The revactormay'contain no' packing,"or may be packedV with i' catalytically inert solid material, as ceramic rings, pumice, 'and the like.

:Reactor '1 -is preferablyoperated'at avv temperature of from about 250450'F.,"'dependingupon the' nature `of the olein -feed and otherv reaction conditions. The rate of flow of synthesis gases 4and'oleiins through reactor VSi is so regulated"thatthe desired conversion level of the oleiinic material is obtained.l

A mixture of liquid oxygenated reaction products containing in solution unreacted oleiins, dissolved catalyst, unreacted synthesis gases, andsecondary reaction produets is withdrawn overhead from reactor lfand is transferred through line 8,' and cooler 10, and line 12, to high pressure separator 14, where unrea'cted` gases are withdrawn overhead through line 16, scrubbedin scrubber i@ of entrained, liquid, and used in anyway desired. They may be recycled to synthesisgas feed line 4 via line 20 for use in adjusting Vthe desired H2 partial pressure andfor adjusting the Hz/CO ratio in 'the feed vto reactor =1. If

,desifsdtealy a Part sf @sans .fram seaftortmay bethus'emplyed. Thebalan'ce may'bepurgged from the 'systmarmigh`1ine'zz-ll j, a j

A 'stream of ,liquid mixture comprising rprimary reactin product, iii-icon.vetted 'oletiusjand' secondary reaction products," and containing relatively," high concentra- 'tionss of cobalt carbonyl aswell fas/other cobalt com- Vpounds and `complexes,"and which"maycontain upto 3% or more water, resulting atleast"infpmt'ifromfsecndary reactionsfas described heretofore, is withdrawn from sepa- :r'ator14 through line ,24.* "Afport'ionlof said"withdrawn stream maybe recycled, desired,'to Vreactor 1 via line 26 to aid in cooling and'maintenance of temperature con- -t'rol ofthe primary carbonylatio'n stage. The `balance of lthe primary reaction product may be Withdrawn through line 28, pressure release `valve 29, and thence to vdecobalti'ng zone 30Wherein by suitable 'heat treatment at "about-'0-400"F., thedissolved cobalt carbonyl is decomposed to metallic cobaltand cobalt compounds. A stream offhydrogencomprising gas may -be admitted through line 32 to aid in stripping' andremoving CO re- "sulting from the decomposition of themetal carbonyl.

'Zone 30 'may be operated at high4 pressure, though prestreatment :with'wa'ten steam, 'or dilute' organic acids, may

`also 'ber employed.

; drawn through line 36 and may be passed to lter 3$-for removal of suspended solids, thence through lineV `39to the lower portion of fixed bed hydrogenator 40. Simultaneously, hydrogeny is supplied to reactor 40 through line 42 in proportions sufficient to convert the aldehyde product to alcohols. Reactor 40 contains a fixed bed of hydrogenation catalyst prepared in the mannery as described above. Suitable Voperating conditions include pressures of,20004000 p. s. i. g., and temperatures-of from 300-500 F., depending upon the naturevof the aldehyde product being treated. Feed rates (liquid) of about 0.25-1.5 v./v./hr. and H2 feed ratel lof 5,000- 10,000 standard cubic feet/barrel ofliquid feed may -be employed.

Preferably, water is injected 4into hydrogenator 40 through line e3 and pump 45. The amountofjwater added may be as much as 10 vol. percentY of the liquid feed to hydrogenator 40. Water additionirnayhecntinuous or intermittent. The rate of` addition is determined to some extent by vthe'rate of decobalter feed addition, and the water may, if desired, be preheated prior to injection. The catalyst of thepresent invention, because of its ruggedness, permits this beneficial injection of water. Other catalysts, as shown subsequently, are'rapidly deactivated and disintegrated bythe presence of Water. Water may increase the alcohol selectivity 10% or even higher. However, it may Anot under certain circumstances,'be necessary or desirabl to add water.

The products vof the hydrogenationreaction'iriay Abe withdrawn overhead through line 54,' then thioughf'cooler S6 into high pressure separator. 5S, where unreacted' hy- Y drogen may be withdrawn overheadftlirugh linef60 lf r Vfurtheruse in the system, ifV desired. Liquid'prdiicts "are withdrawn from liquid-gasnsepar'ator 58 through line '62 and passed to 'settler '61, where water'may be vwithdrawn through line 63, and the upper `alcohol#containin'g layer passed to hydrocarbon still 64,`where low-boiling products, mostly hydrocarbons boiling belowl the alcohol product desired are distilled overhead. Thusfwhen C7 olefin fraction is the feed Vto carhonylatin reactor,"'gen lerally vthe product boiling up to 340]F. is vr'en'rovedas a heads cut in hydrocarbon'still 64. "Thismat'erial may be Withdrawn overhead through line 66 and may be used as a gasoline blending agent. The bottoms from this primary distillate'are withdrawn from st`il1`64 and sent through line 68 to alcohol still 70 where product` OXOALDEHYDE FEED e-HOUR .au'rooinivnV HYDRoGENATroN 350 F., asco-zwaard.

A B C D Aldehyde Type Ca Os j 4C5 Catalyst Binder Al `Al None None Wt. Percent Binder 10 .20 Wt Percent Water on Feed.. 10 10 l 0 Product Carbouyl No 1.6 Y1.0 0.7 1 0 7 Weight Percent Alcohol Yield 69 66 56.7 Used Catalyst-Side Crushing Strength, Lbs.: v

-,Maximum 14 26 10 4 Minimum 6 v 14 4 2 Average 11 20. 2 632 '.3. 2

1 Aldehyde reduction-at 1800 p. s. 1i g.

` lhour autoclave operation,

' 4The aluminum bonded catalyst may be `particularly beneficially employed in the presenceV of water and a comparable degree of hydrogenation is obtained as evaluated bythecarbonyl number. Furthermore, because of Vthe beneficial eiect of the added water, a considerably enhanced valcoholyieldV is realized. The eiect of water on unbonded nickel is shown in columns C and D above, fand it is seen that the aluminum bonded catalysts, even after operation with 10% water in the feed, was stronger ,than the unbonded catalysts after operation Without the thefollowing data: v `HYDBOGENAT10N 0F Cs 0X0 PRODUCT ((10% ADDED l l WATER) Z600-2800 p. s. l. g., 350 F. Commercial nlckelcatalyst pilledwith 10% aluminum.)

Not only is copper chromite a better catalyst when bonded in accordance with the present invention than the unbonded material, but also, the aluminum bonded copper chromite is far/superior to the same catalyst `bonded by such agents as, for instance, sodium silicate.

In Example II, below, there are shown results obtained whena copper chromite catalyst prepared in the conventional manner, described in detail below, is bonded with aluminum and when a similar catalyst is bonded with sodium silicate. Not only are higher crushing strengths obtained by the productof the invention, but also, lower carbonyl numbers are realized.

Example Il `AUTOCLAVE HYDROGENATION OF Cr ALDEHYDE (10% DDED WATER) [Copper chromite catalyst (20 wt. percent on feed). -hour operation .s.1.g.,45oF.1

catalyst Binder ahniim sndium silicate Product oubonyi No a 1.1 s. e Used Catalyst Insp-Avg. Side Crushing Strength, Lbs.` 11.8 1. 8 2

'I'he binder is usually expressed on the basis of active component composition, that is, copper chromite with 20%ialuminum consists of a hundred parts of copper chromite and twenty parts of aluminum@ It is normally desirable to keep the amount of binder to a'minimum and, although aluminum in 20% concentration has been used above and shown to give excellent results, a 10% concentration also has been found to operate satisfactorily.

`In general, the final catalyst composition comprises 100 parts of active catalyst plus the minimum parts of powdered metal which is found effective to extend the useful life f the catalyst.

Although, because of the lack ofV strength of the unbondedcopper chromite, it has not been found feasible to maintain a continuous unit in operation therewith, because it was not possible to'maintain contact between catalyst and reactants, it has been found possible to comi pare in a continuous operation the aluminum bonded. copper chromite embodiment of the present invention with a copper chromite catalyst supported `on silica gel. A

. in three portions in a casserole over a free llame.

copper chromite-silica gel catalyst was prepared from` copper nitrate and chromium trioxide. Also, a copper chromite catalyst was prepared from the same starting materials, but silica gel was replaced by an aluminum binder. As will be seen in Example III below, the silica gel-supported copper catalyst gave very poor results in the continuous operation whereas the preparation of the invention gave excellent performance in the hydrogenation of both amyl and octyl aldehydes.

Example III Copper Copper Chromite Chi-omite Catalyst Silica Gel Aluminum Run No A B C Run Home l-10 1-8 8996 Catalyst Age, Hr 53. 5 112 245 0x0 Product C C: C; Temperature, Fa 451 443 437 Liquid Feed Rate, v./v./hr 0. 49 0. 5 0.5 Product Carbonyl No. 127 2. 6 7 selectivity, Mole Percent Alcohols 34 80.2 75. 9

In another set of experiments, the aluminum bonded copper chromite catalyst above was purposely-poisoned with sulfur which decreased its activity, but as shown in Example IV, below, in spite of this poisoning, its performance is superior vto that of an unbonded nickel catalyst which was not likewise sulfur poisoned.

Example IV CONTINUOUS UNIT HYDROGENATION OF Cn OXO ALDEHYDES [Commercial hydrogen] Catalyst.. Nickel-Kiesel- Copper Chro- (20% Al guhr mite Binder) Catalyst Age, Hr 177 193 112 245 374 Temperature, F. 425 449 443 437 500 Feed Rate, V./V./h1' 0. 9 1.0 0.5 0.6 0.5 Water Rate, Percent- 6 5 5 5 5 Carbonyl No 14 7 2. 6 7 13 Total Catalyst Age, Hrs. 193 374 PREPARATION A Nine hundred ml. of solution (at 80 C.) containing 260 g. of trihydrated copper nitrate and 31 g. of barium nitrate were added to 900 ml. of a solution (at 250 C.) containing 151 g. of ammonium dichromate and 225 ml. of 28 percent ammonium hydroxide. The precipitate was filtered, pressed, and sucked as dry as possible. The product was dried in an oven at C. to 80 C. for twelve hours and then pulverized. It was decomposed In carrying out the decomposition, the powder was continuously stirred with a spatula and the heating so regulated that the evolution of gases did not become violent. During this process the color of the powder changed from orange to brown and finally to black. When the entire mass had become black, the evolution of gases ceased, and the powder was removed from the casserole and allowed to cool. The combined product was then leached for thirty minutes with 600 ml.- of 10% acetic acidsolution, filtered,

and Washed with 600 ml. of water in six portions, dried for twelve hours at 125 C., and pulverized. The yield of catalyst was 170 g. The temperature of decomposition must be carefully controlled in order to produce a highly active, uniform product.

The nal product prio-r to metal bonding had the following composition:

'Percent BaO 9.4 CuO 44.0

CrgOB 46.6

PREPARATION B 5061 grams copper nitrate and 2099 grams chromic acid were dissolved in 8400 cc. of distilled water. The materials were stirred in a crock until solution was complete.

4778 cc. of 28% ammonium hydroxide were slowly added with stirring. The slurry was then agitated for one hour. Filtration was carried out in a vacuum Buchner funnel. The filter cake was reslurried in 12 liters of hot distilled water. The slurry was filtered and the cake dried at 250 F. After drying over night, the whole was put through a four-mesh screen and returned to evaporating dishes and further dried over night. Decomposition was effected in an eight-inch evaporating dish over an open flame. A KA2 wire screen, 100-mesh, was used to cover the dish to prevent powder from blowing out during decomposition. After the initial decomposition was complete the catalyst was heated to 1200 F. in an electric mufe furnace.

Yield: 2903 grams.

The ignited material was thereafter mixed with aluminum powder in the ratio of 4:1 and was pilled into 1A pellets. The pellets were then heated in the presence of hydrogen for 4 hours at a temperature of 1200 F., thereby causing bonding to occur at ornear the activation temperature of the catalyst.

The bonded nickel catalysts were prepared by decomposing nickel carbonate supportedfon kieselguhr (70% nickel reduced metal basis). The carbonate is decomposedby roasting at about 850 F., thereafter the decomposed material was mixed with aluminum powder and pilled.

What is claimed is:

1. In the process for the production of alcohols by catalytic hydrogenation of a liquid carbonylation aldehyde product in the presence of water at temperatures from about 300 F. to about 500 F., and pressures from about 2000 to 4000 p. s. i. g., the improvement which comprises carrying out vsaid hydrogenation with a catalyst prepared by pelleting a hydrogenation catalyst component selected from the class consisting of metal oxides and metals from reduced metal oxides mixed with finely divided aluminum, aluminum having a sintering point at a temperature in the range of the activation temperature of the catalyst, 850 to 1200l F., and heating the resulting pellet in the presence of hydrogen at temperatures in the range of about 850 to 1200 F. so that the finely divided aluminum becomes sintered and bonded to the catalyst component in the pellets, thereby producing a catalyst of high strength and of undiminished catalytic activity.

2. In the process defined by claim 1, the aluminum being present in an amount of l0 to 20 parts per 100 parts by weight of said hydrogenation catalyst component mixed therewith.

3. In the process defined by claim 1, said catalyst being prepared to contain nickel from a reduced nickel oxide as the hydrogenation catalyst component mixed with finely divided aluminum as the bonding metal.

4. In the process defined by claim 1, the hydrogenation catalyst component being copper chromite and the bonding metal being finely divided metallic aluminum.

5. A catalyst which comprises 100 parts of a nickel hydrogenation catalyst pelleted with 10 to 20 parts of finely divided aluminum, the finely divided aluminum being sentered and bonded to the active nickel catalyst.

6. A catalyst which comprises a hydrogenation` catalyst selected from the class consisting of metal oxides and metals from reduced metal oxides pelleted with finely divided aluminum having a sintering point at a temperature in the range of the activation temperature of the hydrogenation catalyst, 850 to 1200 F., said finely divided aluminum being sintered and bonded to the hydrogenation catalyst by a heat treatment of the pellet at said activation temperature range in the presence of hydrogen.

Hill, New York, N. Y., pp. 91, 92, 

1. IN THE PROCESS FOR THE PRODUCTION OF ALCOHOLS BY CATALYTIC HYDROGENATION OF A LIQUID CARBONYLATION ALDEHYDE PRODUCT IN THE PRESENCE OF WATER AT TEMPERATURES FROM ABOUT 300*F. TO ABOUT 500*F., AND PRESSURES FROM ABOUT 2000 P. S. I. G., THE IMPROVEMENT WHICH COMPRISES CARRYING OUT SAID HYDROGENATION WITH A CATALYST PREPARED BY PELLETING A HYDROVENATION CATALYST COMPONENT SELECTED FROM THE CLASS CONSISTING OF METAL OXIDES AND METALS FROM REDUCED METAL OXIDES MIXED WITH FINELY DIVIDED ALUMINUM, ALUMINUM HAVING A SINTERING POINT AT A TEMPERATURE IN THE RANGE OF THE ACTIVATION TEMPERATURE OF THE CATALYST, 850* TO 1200*F., AND HEATING THE RESULTING PELLET IN THE PRESENCE OF HYDROGEN AT TEMPERATURES IN THE RANGE OF ABOUT 850* TO 1200*F. SO THAT THE FINELY DIVIDED ALUMINUM BECOMES SINTERED AND BONDED TO THE CATALYST COMPONENT IN THE PELLETS, THEREBY PRODUCING A CATALYST OF HIGH STRENGH AND OF UNDIMINISHED CATALYTIC ACTIVITY. 